Shell@core-nanostructured TiO(2)@ZnO n-p-n heterojunction nanorods with diameter of 30 nm were successfully fabricated via a hydrothermal method. The photodegradation rate of the TiO(2)@ZnO n-p-n nanorods evaluated by photodegrading methyl orange has been demonstrated to increase three times compared to that of wurtzite hexagonal ZnO. Anatase TiO(2) and Ti(2)O(3) grow along ZnO crystal lattices, which forms p-type Zn(2+) doped Ti(2)O(3) in the interface of TiO(2)/ZnO and therefore numerous n-p-n heterojunctions owing to the substitution of Ti(3+) by Zn(2+). Under the drive of inner electric field, the photogenerated electrons are both injected to the conduction band of Zn(2+) doped Ti(2)O(3) from conduction bands of ZnO and TiO(2), which efficiently enhances the separation of photogenerated electron-hole pairs and accelerates the transport of charges. The results suggest that TiO(2)@ZnO n-p-n heterojunction nanorods are very promising for enhancing the photocatalytic activity of photocatalysts.